Photoelectric conversion element, photoelectric conversion module, and solar photovoltaic power generation system

ABSTRACT

There is provided a photoelectric conversion element which can prevent the contact resistance between a non-crystalline semiconductor layer containing impurities and an electrode formed on the non-crystalline semiconductor layer from increasing, and can improve the element characteristics. A photoelectric conversion element ( 10 ) includes a semiconductor substrate ( 12 ), a first semiconductor layer ( 20   n ), a second semiconductor layer ( 20   p ), a first electrode ( 22   n ), and a second electrode ( 22   p ). The first semiconductor layer has a first conductive type. The second semiconductor layer has a second conductive type. The first electrode is formed on the first semiconductor layer. The second electrode is formed on the second semiconductor layer. The first electrode includes a first transparent conductive layer ( 26   n ) formed on the first semiconductor layer, and a first metal layer ( 28   n ) formed on the first transparent conductive layer. The first metal layer includes a plurality of metal crystal grains in which the average crystal grain size in the in-surface direction of the first metal layer is greater than the thickness of the first metal layer.

This application is the U.S. national phase of International Application No. PCT/JP2014/078384 filed 24 Oct. 2014 which designated the U.S. and claims priority to JP Patent Application No. 2013-222818 filed 25 Oct. 2013, the entire contents of each of which are hereby incorporated by reference.

TECHNICAL FIELD

The present invention relates to a photoelectric conversion element, a photoelectric conversion module, and a solar photovoltaic power generation system.

BACKGROUND ART

In recent years, a solar battery which serves as a photoelectric conversion element has drawn attention. An example of the solar battery is a rear surface electrode type solar battery.

The rear surface electrode type solar battery is disclosed in Japanese Unexamined Patent Application Publication No. 2007-281156. In the related art, the rear surface electrode type solar battery includes a crystalline semiconductor; an n-type non-crystalline semiconductor layer which is formed on a rear surface which is opposite to an irradiation surface of sunlight, in the crystalline semiconductor; a p-type non-crystalline semiconductor layer which is formed on the rear surface; and electrodes which are formed on the n-type non-crystalline semiconductor layer and the p-type non-crystalline semiconductor layer.

However, as described in the related art, in a case where the electrodes are formed on the non-crystalline semiconductor layers, there is a problem that the contact resistance between the non-crystalline semiconductor layer and the electrode increases.

SUMMARY OF INVENTION

An object of the present invention is to provide a photoelectric conversion element which can reduce the contact resistance between a non-crystalline semiconductor layer containing impurities and an electrode formed on the non-crystalline semiconductor layer, and can improve the element characteristics.

A photoelectric conversion element according to embodiments of the present invention includes: a semiconductor substrate, a first semiconductor layer, a second semiconductor layer, a first electrode, and a second electrode. The first semiconductor layer has a first conductive type. The second semiconductor layer has a second conductive type opposite to the first conductive type. The first electrode is formed on the first semiconductor layer. The second electrode is formed on the second semiconductor layer. The first electrode includes a first transparent conductive layer and a first metal layer. The first transparent conductive layer is formed on the first semiconductor layer. The first metal layer is formed on the first transparent conductive layer. The first metal layer includes a plurality of metal crystal grains in which the average crystal grain size in the in-surface direction of the first metal layer is greater than the thickness of the first metal layer.

The photoelectric conversion element according to the embodiments of the present invention can prevent the contact resistance between a non-crystalline semiconductor layer containing impurities and an electrode formed on the non-crystalline silicon layer from increasing, and can improve the element characteristics.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a sectional view illustrating a schematic configuration of a photoelectric conversion element according to a first embodiment of the present invention.

FIG. 2A is a sectional view illustrating a manufacturing method of a photoelectric conversion element illustrated in FIG. 1, and is a sectional view illustrating a silicon substrate.

FIG. 2B is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 1, and is a sectional view illustrating a state where an intrinsic non-crystalline silicon layer is formed on the rear surface of the silicon substrate and an n-type non-crystalline silicon layer and a p-type non-crystalline silicon layer are formed on the intrinsic non-crystalline silicon layer.

FIG. 2C is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 1, and is a sectional view illustrating a state where a passivation film is formed on a light-receiving surface of the silicon substrate.

FIG. 2D is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 1, and is a sectional view illustrating a state where a reflection prevention film is formed on the passivation film.

FIG. 2E is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 1, and is a sectional view illustrating a state where a transparent conductive layer and a metal film are formed.

FIG. 2F is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 1, and is a sectional view illustrating a state where an electrode is formed.

FIG. 3 is a graph illustrating a relationship between an average crystal grain size and the annealing temperature.

FIG. 4 a graph illustrating a relationship between the average crystal grain size and contact resistance.

FIG. 5 is a sectional view illustrating a schematic configuration of a sample when the contact resistance is measured.

FIG. 6 is a schematic view illustrating an interface level of a metal crystal grain.

FIG. 7 is a band diagram of the interface between the electrode and the n-type non-crystalline silicon layer in a case where the metal crystal grain is small.

FIG. 8 is a band diagram of the interface between the electrode and the n-type non-crystalline silicon layer in a case where the metal crystal grain is large.

FIG. 9 is a graph illustrating a relationship between cell resistance and an average value of the average crystal grain size.

FIG. 10 is a graph illustrating a relationship between conversion efficiency η and the average value of the average crystal grain size.

FIG. 11 is a graph illustrating a relationship between a curve factor FF and the average value of the average crystal grain size.

FIG. 12 is a sectional view illustrating an example of a schematic configuration of a photoelectric conversion element according to an application example 1 of a first embodiment of the present invention.

FIG. 13 is a sectional view illustrating an example of a schematic configuration of a photoelectric conversion element according to an application example 2 of the first embodiment of the present invention.

FIG. 14 is a sectional view illustrating an example of a schematic configuration of a photoelectric conversion element according to an application example 3 of the first embodiment of the present invention.

FIG. 15 is a sectional view illustrating a schematic configuration of a photoelectric conversion element according to a second embodiment of the present invention.

FIG. 16A is a sectional view illustrating a manufacturing method of the photoelectric conversion element illustrated in FIG. 15, and is a sectional view illustrating a state where an n-type diffusion layer is formed on the rear surface side of the silicon substrate.

FIG. 16B is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 15, and is a sectional view illustrating a state where an insulation film is formed on the rear surface of the silicon substrate.

FIG. 16C is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 15, and is a sectional view illustrating a state where a p-type diffusion layer is formed on the front surface side of the silicon substrate.

FIG. 16D is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 15, and is a sectional view illustrating a state where a non-crystalline film is formed on the light-receiving surface of the silicon substrate.

FIG. 16E is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 15, and is a sectional view illustrating a state where the non-crystalline film is formed on a passivation film.

FIG. 16F is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 15, and is a sectional view illustrating a state where the metal film is formed.

FIG. 16G is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 15, and is a sectional view illustrating a state where the electrode is formed.

FIG. 17 is a sectional view illustrating a schematic configuration of a photoelectric conversion element according to an application example of the second embodiment of the present invention.

FIG. 18 is a sectional view illustrating a schematic configuration of a photoelectric conversion element according to a third embodiment of the present invention.

FIG. 19A is a sectional view illustrating a manufacturing method of the photoelectric conversion element illustrated in FIG. 18, and is a sectional view illustrating a state where the n-type diffusion layer is formed on the rear surface side of the silicon substrate.

FIG. 19B is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 18, and is a sectional view illustrating a state where the p-type diffusion layer is formed on the front surface side of the silicon substrate.

FIG. 19C is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 18, and is a sectional view illustrating a state where the non-crystalline film is formed on the front surface of the silicon substrate.

FIG. 19D is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 18, and is a sectional view illustrating a state where the non-crystalline film is formed on the rear surface of the silicon substrate.

FIG. 19E is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 18, and is a sectional view illustrating a state where the metal film is formed.

FIG. 19F is a sectional view illustrating the manufacturing method of the photoelectric conversion element illustrated in FIG. 18, and is a sectional view illustrating a state where the electrode is formed.

FIG. 20 is a sectional view illustrating a schematic configuration of a photoelectric conversion element according to an application example 1 of the third embodiment of the present invention.

FIG. 21 is a sectional view illustrating a schematic configuration of a photoelectric conversion element according to an application example 2 of the third embodiment of the present invention.

FIG. 22 is a sectional view illustrating a configuration of a photoelectric conversion module provided with the photoelectric conversion element according to the embodiment.

FIG. 23 is a schematic view illustrating a configuration of a solar photovoltaic power generation system provided with the photoelectric conversion element according to the embodiment.

FIG. 24 is a schematic view illustrating a configuration of a photoelectric conversion module array illustrated in FIG. 23.

FIG. 25 is a schematic view illustrating a configuration of the solar photovoltaic power generation system provided with the photoelectric conversion element according to the embodiment.

DESCRIPTION OF EMBODIMENTS

A photoelectric conversion element according to embodiments of the present invention includes: a semiconductor substrate, a first semiconductor layer, a second semiconductor layer, a first electrode, and a second electrode. The first semiconductor layer has a first conductive type. The second semiconductor layer has a second type opposite to the first conductive type. The first electrode is formed on the first semiconductor layer. The second electrode is formed on the second semiconductor layer. The first electrode includes a first transparent conductive layer and a first metal layer. The first transparent conductive layer is formed on the first semiconductor layer. The first metal layer is formed on the first transparent conductive layer. The first metal layer includes a plurality of metal crystal grains in which the average crystal grain size in the in-surface direction of the first metal layer is greater than the thickness of the first metal layer.

In the first aspect, it is possible to reduce the contact resistance between the first semiconductor layer and the first electrode formed on the first semiconductor layer. As a result, it is possible to improve the characteristics of the photoelectric conversion element.

In addition, the first electrode has a structure in which the first transparent conductive layer and the first metal layer are layered in order. Therefore, in a case where the first electrode is disposed on the rear surface side of the semiconductor substrate, reflectivity becomes high on the rear surface side of the semiconductor substrate. As a result, short-circuit in photoelectric current increases. Therefore, it is possible to improve the characteristics of the photoelectric conversion element.

In the photoelectric conversion element according to a second aspect of the present invention, in the photoelectric conversion element according to the first aspect, the first metal layer has silver as a main component.

In the second aspect, it is possible to reduce resistance of the first metal layer. In addition, in a case where the first electrode is formed on the rear surface opposite to a light-incident side of the semiconductor substrate, by effectively reflecting light reaching the rear surface, conversion efficiency is improved.

In the photoelectric conversion element according to a third aspect of the present invention, in the photoelectric conversion element according to the first or second aspect, the first semiconductor layer and the second semiconductor layer are formed on the rear surface opposite to a light-receiving surface on the semiconductor substrate.

In the third aspect, in the rear surface electrode type photoelectric conversion element, it is possible to improve the element characteristics.

In the photoelectric conversion element according to a fourth aspect of the present invention, in the photoelectric conversion element according to any of the first to third aspects, in the metal crystal grains, a crystal axis which is parallel to the thickness direction of the semiconductor substrate is preferentially oriented in the <111> direction.

In the fourth aspect, it is possible to prevent the contact resistance between the first electrode and the first semiconductor layer from increasing.

In the photoelectric conversion element according to a fifth aspect of the present invention, in the photoelectric conversion element according to any of the first to fourth aspects, the first conductive type is an n-type, and the average crystal grain size is less than 3.33 times the thickness of the first metal layer.

In the fifth aspect, it is possible to prevent the contact resistance between the first electrode and the first semiconductor layer from increasing.

In the photoelectric conversion element according to a sixth aspect of the present invention, in the photoelectric conversion element according to any of the first to fourth aspects, the first conductive type is the n-type, and the average crystal grain size is 2.85 times or less than the thickness of the first metal layer.

In the sixth aspect, it is possible to further prevent the contact resistance between the first electrode and the first semiconductor layer from increasing.

In the photoelectric conversion element according to a seventh aspect of the present invention, in the photoelectric conversion element according to any of the first to fourth aspects, the first conductive type is the n-type, and the average crystal grain size is 1.55 times or greater and 2.85 times or less than the thickness of the first metal layer.

In the seventh aspect, it is possible to still further prevent the contact resistance between the first electrode and the first semiconductor layer from increasing.

In the photoelectric conversion element according to an eighth aspect of the present invention, in the photoelectric conversion element according to any of the first to fourth aspects, the first conductive type is a p-type, and the average crystal grain size is 3.3 times or less than the thickness of the first metal layer.

In the eighth aspect, it is possible to prevent the contact resistance between the first electrode and the first semiconductor layer from increasing.

In the photoelectric conversion element according to a ninth aspect of the present invention, in the photoelectric conversion element according to any of the first to fourth aspects, the first conductive type is a p-type, and the average crystal grain size is 1.03 times or greater and 2.95 times or less than the thickness of the first metal layer.

In the ninth aspect, it is possible to further prevent the contact resistance between the first electrode and the first semiconductor layer from increasing.

In the photoelectric conversion element according to a tenth aspect of the present invention, in the photoelectric conversion element according to any of the first to fourth aspects, the first conductive type is the p-type, and the average crystal grain size is 1.53 times or greater and 2.15 times or less than the thickness of the first metal layer.

In the tenth aspect, it is possible to still further prevent the contact resistance between the first electrode and the first semiconductor layer from increasing.

In the photoelectric conversion element according to an eleventh aspect of the present invention, in the photoelectric conversion element according to any of the first to fourth aspects, a second electrode includes a second transparent conductive layer formed on the second semiconductor layer, and a second metal layer formed on the second transparent conductive layer. The second metal layer includes a plurality of metal crystal grains. A contact area between the second electrode and the second semiconductor layer is 1 times or greater than the contact area between the first electrode and the first semiconductor layer. An average value of the average crystal grain size of the metal crystal grain in the first metal layer, and the average crystal grain size of the metal crystal grain in the second metal layer, is 1.03 times or grater and 2.15 times or less than the thickness of the first metal layer and the second metal layer.

In the eleventh aspect, it is possible to improve the element characteristics.

In the photoelectric conversion element according to a twelfth aspect of the present invention, in the photoelectric conversion element according to the first aspect, the first semiconductor layer is formed on the semiconductor substrate, and includes a first conductive type non-crystalline semiconductor. Between the semiconductor substrate and the first semiconductor layer, a third semiconductor layer including an intrinsic non-crystalline semiconductor is formed.

In the twelfth aspect, compared to a case where the first semiconductor layer is formed directly on the semiconductor substrate, the passivation characteristics of the rear surface of the semiconductor substrate is improved.

In the photoelectric conversion element according to a thirteenth aspect of the present invention, in the photoelectric conversion element according to the twelfth aspect, the intrinsic non-crystalline semiconductor is hydrogenated amorphous silicon.

In the thirteenth aspect, the passivation characteristics of the rear surface of the semiconductor substrate is further improved.

In the photoelectric conversion element according to a fourteenth aspect of the present invention, in the photoelectric conversion element according to the twelfth aspect, the first conductive type non-crystalline semiconductor is hydrogenated amorphous silicon.

In the fourteenth aspect, it is possible to suppress deterioration of contact interface between the first electrode and the first semiconductor layer.

In the photoelectric conversion element according to a fifteenth aspect of the present invention, in the photoelectric conversion element according to the first aspect, the second electrode includes the second transparent conductive layer and the second metal layer. The second transparent conductive layer is formed on the second semiconductor layer. The second metal layer is formed on the second transparent conductive layer. The second metal layer includes a plurality of metal crystal grains in which the average crystal grain size in the in-surface direction of the second metal layer is greater than the thickness of the second metal layer.

In the fifteenth aspect, it is possible to decrease the contact resistance between the second semiconductor layer and the second electrode formed on the second semiconductor layer. As a result, it is possible to further improve the characteristics of the photoelectric conversion element.

In the photoelectric conversion element according to a sixteenth aspect of the present invention, in the photoelectric conversion element according to the fifteenth aspect, the second semiconductor layer is formed to be in contact with the semiconductor substrate, and includes a second conductive type non-crystalline semiconductor. Between the semiconductor substrate and the second semiconductor layer, a fourth semiconductor layer including the intrinsic non-crystalline semiconductor is formed.

In the sixteenth aspect, compared to a case where the second semiconductor layer is formed directly on the semiconductor substrate, the passivation characteristics of the rear surface of the semiconductor substrate is improved.

In the photoelectric conversion element according to a seventeenth aspect of the present invention, in the photoelectric conversion element according to the sixteenth aspect, the intrinsic non-crystalline semiconductor is hydrogenated amorphous silicon.

In the seventeenth aspect, the passivation characteristics of the rear surface of the semiconductor substrate is further improved.

In the photoelectric conversion element according to an eighteenth aspect of the present invention, in the photoelectric conversion element according to the sixteenth aspect, the second conductive type non-crystalline semiconductor is hydrogenated amorphous silicon.

In the eighteenth aspect, it is possible to suppress the deterioration of the contact interface between the second electrode and the second semiconductor layer.

A photoelectric conversion module according to the first aspect of the present invention includes the photoelectric conversion element according to any of the first to eighteenth aspects of the present invention.

In the first aspect, it is possible to improve performance of the photoelectric conversion module.

A photoelectric conversion system according to the first aspect of the present invention includes the photoelectric conversion module according to the first aspect of the present invention.

In the first aspect, it is possible to improve performance of the photoelectric conversion system.

Hereinafter, more specific embodiments of the present invention will be described with reference to the drawings. The same parts or the same corresponding parts in the drawings will be given the same reference numerals, and the description thereof will not be repeated.

First Embodiment

FIG. 1 illustrates a photoelectric conversion element 10 according to a first embodiment of the present invention. The photoelectric conversion element 10 is the rear surface electrode type solar battery.

The photoelectric conversion element 10 includes a silicon substrate 12, a passivation film 14, a reflection preventing film 16, intrinsic non-crystalline silicon layers 18 and 19, an n-type non-crystalline silicon layer 20 n, a p-type non-crystalline silicon layer 20 p, an electrode 22 n, and an electrode 22 p.

The silicon substrate 12 is an n-type single crystal silicon substrate. The thickness of the silicon substrate 12 is, for example, 50 μm to 300 μm. The specific resistance of the silicon substrate 12 is, for example, 1.0 Ω·cm to 10.0 Ω·cm. In addition, instead of the n-type single crystal silicon substrate, an n-type polycrystal silicon substrate, an n single crystal germanium, or an n-type single crystal silicon germanium, may be used, and in general, the semiconductor substrate may be used. Instead of the n-type, the p-type may be used.

Although not illustrated, a texture structure is formed on the light-receiving surface of the silicon substrate 12. Accordingly, the light which is incident on the silicon substrate 12 is blocked up, and the use efficiency of the light can be improved.

It is preferable that the orientation of the silicon substrate 12 is (100). Accordingly, it becomes easy to form the texture structure.

The light-receiving surface of the silicon substrate 12 is covered with the passivation film 14. The passivation film 14 is, for example, a hydrogenated amorphous silicon film. The film thickness of the passivation film 14 is, for example, 3 nm to 30 nm. In addition, as the passivation film 14, instead of the hydrogenated amorphous silicon film, a silicon nitride film, a silicon oxide film, or a silicon oxynitride film, may be used.

The reflection preventing film 16 covers the passivation film 14. The reflection preventing film 16 is, for example, a silicon nitride film. The film thickness of the reflection preventing film 16 is, for example, 50 nm to 200 nm.

On the rear surface of the silicon substrate 12, the intrinsic non-crystalline silicon layers 18 and 19 are formed. The intrinsic non-crystalline silicon 18 and 19 are made of, for example, an i-type hydrogenated amorphous silicon (a-Si:H). The intrinsic non-crystalline silicon layer 18 is formed at a part of the rear surface of the silicon substrate 12. The intrinsic non-crystalline silicon layer 19 is formed to be adjacent to the intrinsic non-crystalline silicon layer 18 on the rear surface of the silicon substrate 12. In other words, the intrinsic non-crystalline silicon layers 18 and 19 are alternately formed on the entire rear surface of the silicon substrate 12. The thickness of the intrinsic non-crystalline silicon layers 18 and 19 is, for example, 10 nm. In the example illustrated in FIG. 1, the intrinsic non-crystalline silicon layer 19 is formed to be adjacent to the intrinsic non-crystalline silicon layer 18, but, for example, may be formed at a part of the region in which the intrinsic non-crystalline silicon layer 18 is not formed on the rear surface of the silicon substrate 12. In addition, the intrinsic non-crystalline silicon layers 18 and 19 may be made only of a non-crystalline phase, or may be made of a fine crystalline phase and a non-crystalline phase.

On the intrinsic non-crystalline silicon layer 18, the n-type non-crystalline silicon layer 20 n is formed. The n-type non-crystalline silicon layer 20 n is made of the hydrogenated amorphous silicon (a-Si:H(n)) containing n-type impurities (for example, phosphorus). The thickness of the n-type non-crystalline silicon layer 20 n is, for example, 10 nm. The impurities concentration of the n-type non-crystalline silicon layer 20 n is, for example, 1×10¹⁹ cm⁻³ to 1×10²¹ cm⁻³. The n-type non-crystalline silicon layer 20 n may be made only of the non-crystalline phase, or may be made of the fine crystalline phase and the non-crystalline phase. An example of a case where the n-type non-crystalline silicon layer 20 n is made of the fine crystalline phase and the non-crystalline phase, is, for example, an n-type microcrystalline silicon.

On the intrinsic non-crystalline silicon layer 19, the p-type non-crystalline silicon layer 20 p is formed. The p-type non-crystalline silicon layer 20 p is made of the hydrogenated amorphous silicon (a-Si:H(p)) containing p-type impurities (for example, boron). The thickness of the p-type non-crystalline silicon layer 20 p is, for example, 10 nm. The impurities concentration of the p-type non-crystalline silicon layer 20 p is, for example, 1×10¹⁹ cm⁻³ to 1×10²¹ cm⁻³. The p-type non-crystalline silicon layer 20 p may be made only of the non-crystalline phase, or may be made of the fine crystalline phase and the non-crystalline phase. An example of a case where the p-type non-crystalline silicon layer 20 p is made of the fine crystalline phase and the non-crystalline phase, is a p-type microcrystalline silicon. In the example illustrated in FIG. 1, the n-type non-crystalline silicon layer 20 n is formed to be adjacent to the p-type non-crystalline silicon layer 20 p, but it is not necessary to be adjacent to the p-type non-crystalline silicon layer 20 p, and for example, the n-type non-crystalline silicon layer 20 n may be formed at least at a part on the non-crystalline silicon layer 18, or the p-type non-crystalline silicon layer 20 p may be formed at least at a part on the non-crystalline silicon layer 19.

In the in-surface direction of the silicon substrate 12, it is preferable that the width dimension of the n-type non-crystalline silicon layer 20 n is less than the width dimension of the p-type non-crystalline silicon layer 20 p. As a ratio of the area of the p-type non-crystalline silicon layer 20 p with respect to the sum of the area of the n-type non-crystalline silicon layer 20 n and the area of the p-type non-crystalline silicon layer 20 p (area ratio of the p-type non-crystalline silicon layer 20 p) increases, the distance by which the light-generated minority carrier (positive hole) should move to reach the p-type non-crystalline silicon layer 20 p decreases. Therefore, the number of recombining positive holes until reaching the p-type non-crystalline silicon layer 20 p decreases, and the short-circuit in photoelectric current increases. Therefore, a conversion ratio of the photoelectric conversion element 10 is improved. A preferable area ratio of the p-type non-crystalline silicon layer 20 p is 63% to 90%.

Although not illustrated, the texture structure may be formed on the rear surface of the silicon substrate 12. In this case, in the intrinsic non-crystalline silicon layers 18 and 19, and the n-type non-crystalline silicon layer 20 n and the p-type non-crystalline silicon layer 20 p, unevenness which corresponds to the texture structure of the rear surface of the silicon substrate 12 is formed.

On the n-type non-crystalline silicon layer 20 n, the electrode 22 n is formed. The electrode 22 n includes a transparent conductive layer 26 n and a metal layer 28 n. The transparent conductive layer 26 n is made of, for example, ITO. The thickness of the transparent conductive layer 26 n is, for example, 0.1 nm to 20 nm. The metal layer 28 n has silver as a main component. The metal layer 28 n may contain metal (for example, titanium) other than silver. The thickness of the metal layer 28 n is, for example, 100 nm to 1000 nm.

On the p-type non-crystalline silicon layer 20 p, the electrode 22 p is formed. The electrode 22 p includes a transparent conductive layer 26 p and a metal layer 28 p. The transparent conductive layer 26 p is made of, for example, ITO. The thickness of the transparent conductive layer 26 p is, for example, 0.1 nm to 20 nm. The metal layer 28 p has silver as a main component. The metal layer 28 p may contain metal (for example, titanium) other than silver. The thickness of the metal layer 28 p is, for example, 100 nm to 1000 nm.

In addition, in a case where the texture structure is formed on the rear surface of the silicon substrate 12, adhesiveness between the electrode 22 n and the n-type non-crystalline silicon layer 20 n and adhesiveness between the electrode 22 p and the p-type non-crystalline silicon layer 20 p are improved. Accordingly, yield and reliability of the photoelectric conversion element 10 are improved. Furthermore, compared to a case where the rear surface of the silicon substrate 12 is flat, since the contact surface between the electrode 22 n and the n-type non-crystalline silicon layer 20 n, and a contact area between the electrode 22 p and the p-type non-crystalline silicon layer 20 p become large, the contact resistance decreases. In addition, when viewed from the thickness direction of the silicon substrate 12, the texture may be formed in any one of a region including at least a part of the region overlapping the electrode 22 n, and a region including at least a part of the region overlapping the electrode 22 p.

[Manufacturing Method of Photoelectric Conversion Element]

With reference to FIGS. 2A to 2F, a manufacturing method of the photoelectric conversion element 10 will be described.

First, as illustrated in FIG. 2A, the silicon substrate 12 is prepared. The silicon substrate 12 has the texture structure on the entire light-receiving surface. A method for forming the texture structure is, for example, wet etching. By performing the wet etching on the entire light-receiving surface of the silicon substrate 12, the texture structure is formed on the entire light-receiving surface of the silicon substrate 12. The wet etching is performed, for example, by using an alkaline solution. The time for the wet etching is, for example, 10 minutes to 60 minutes. The alkaline solution used in the wet etching is, for example, NaOH or KOH, and the concentration thereof is, for example, 5%.

Next, as will be described in FIG. 2B, intrinsic non-crystalline silicon layers 18 and 19 are formed on the rear surface of the silicon substrate 12, the n-type non-crystalline semiconductor layer 20 n is formed on the intrinsic non-crystalline semiconductor layer 18, and the p-type non-crystalline semiconductor layer 20 p is formed on the intrinsic non-crystalline semiconductor layer 19.

The intrinsic non-crystalline silicon layers 18 and 19 can be formed, for example, by a plasma CVD. In a case where the intrinsic non-crystalline silicon layers 18 and 19 are formed by the plasma CVD, reaction gas which is led into a reaction chamber provided with a plasma CVD device, is silane gas and hydrogen gas. The temperature of the silicon substrate 12 is, for example, 100° C. to 300° C.

Next, the p-type non-crystalline silicon layer is formed on the intrinsic non-crystalline silicon layers 18 and 19. The p-type non-crystalline silicon layer can be formed, for example, by the plasma CVD. In a case where the p-type non-crystalline silicon layer is formed by the plasma CVD, the reaction gas which is led into the reaction chamber provided in the plasma CVD device, is silane gas, hydrogen gas, and diboran gas. The temperature of the silicon substrate 12 is, for example, 100° C. to 300° C.

Next, a coating layer which serves as a mask is formed on the p-type non-crystalline silicon layer. The coating layer is obtained by patterning the silicon nitride film formed on the p-type non-crystalline silicon layer. Instead of the silicon nitride film, the silicon oxide film or the silicon oxynitride film may be used. The patterning is performed, for example, by a photolithography method. The coating layer covers a part which becomes the p-type non-crystalline silicon layer 20 p later, that is, a p-type non-crystalline silicon layer formed on the intrinsic non-crystalline silicon layer 19, on the p-type non-crystalline silicon layer formed on the intrinsic non-crystalline silicon layers 18 and 19.

Next, the p-type non-crystalline silicon layer formed on the intrinsic non-crystalline silicon layer 18 is removed. A method of removing the p-type non-crystalline silicon layer may be dry etching, or may be wet etching. Accordingly, the p-type non-crystalline silicon layer 20 p is formed on the intrinsic non-crystalline silicon layer 19. At this time, the coating layer is formed on the p-type non-crystalline silicon layer 20 p.

Next, an n-type non-crystalline silicon layer is formed on the intrinsic non-crystalline silicon layer 18, and on the coating layer formed on the p-type non-crystalline silicon layer 20 p. The n-type non-crystalline silicon layer can be formed, for example, by the plasma CVD. In a case where the n-type non-crystalline silicon layer is formed by the plasma CVD, the reaction gas which is led into the reaction chamber provided in the plasma CVD device, is silane gas, hydrogen gas, and phosphine gas. The temperature of the silicon substrate 12 is, for example, 100° C. to 300° C.

Next, the coating layer formed on the p-type non-crystalline silicon layer 20 p is removed. Accordingly, the n-type non-crystalline silicon layer 20 n is formed on the intrinsic non-crystalline silicon layer 18. The method of removing the coating layer formed on the p-type non-crystalline silicon layer 20 p is, for example, wet etching.

Next, as illustrated in FIG. 2C, on the light-receiving surface of the silicon substrate 12, the passivation film 14 is formed. The passivation film 14 is formed, for example, by the plasma CVD.

Next, as illustrated in FIG. 2D, the reflection preventing film 16 is formed on the passivation film 14. The reflection preventing film 16 is formed, for example, by forming the silicon nitride film, the silicon oxide film, or the silicon oxynitride film, for example, by the plasma CVD.

Next, as illustrated in FIG. 2E, the transparent conductive layers 26 n and 26 p and metal layers 21 n and 21 p are formed. A forming method of the transparent conductive layers 26 n and 26 p and the metal layers 21 n and 21 p is, for example, as follows.

First, on the n-type non-crystalline silicon layer 20 n and the p-type non-crystalline silicon layer 20 p, by deposition or sputtering, the transparent conductive layer made of ITO and the metal layer made of silver are formed. Next, a resist pattern which serves as a mask is formed on the metal layer. The resist pattern is obtained by patterning the resist formed on the metal layer. The patterning is performed, for example, by the photolithography and etching. In a case of being viewed from the thickness direction of the silicon substrate 12, the resist pattern is formed so as not to overlap a boundary between the n-type non-crystalline silicon layer 20 n and the p-type non-crystalline silicon layer 20 p.

Next, in the transparent conductive layer and the metal layer, a part which is not covered with the resist pattern is removed. A method of removing the transparent conductive layer and the metal layer is, for example, wet etching.

Next, the resist pattern is removed. Accordingly, the transparent conductive layer 26 n and the metal layer 21 n are formed on the n-type non-crystalline silicon layer 20 n, and the transparent conductive layer 26 p and the metal layer 21 p are formed on the p-type non-crystalline silicon layer 20 p. A method of removing the resist pattern is, for example, wet etching.

Next, as illustrated in FIG. 2F, the electrodes 22 n and 22 p are formed. Accordingly, the photoelectric conversion element 10 which is an object is obtained.

The electrodes 22 n and 22 p are formed by performing the heat treatment with respect to the metal films 21 n and 21 p. The heat treatment is performed, for example, by using a hot plate. The time for the heat treatment is, for example, 15 minutes. It is preferable that the temperature of the heat treatment is 100° C. to 200° C. The heat treatment is performed, for example, in the atmosphere. The heat treatment may be performed in the inert atmosphere or in a vacuum. The heat treatment may be performed by some processes, after the metal films 21 n and 21 p are formed. For example, the heat treatment may be performed when a module is manufactured. In addition, after performing the heat treatment or the like and growing the metal crystal grain having a desired size, on the electrodes 22 n and 22 p, the conductive film may further be formed. In this case, it is possible to determine the boundary between the electrode 22 n and the conductive film, and between the electrode 22 p and the conductive film, from discontinuity of distribution of the metal crystal grain, discontinuity of composition, or the like.

[Average Crystal Grain Size]

In the photoelectric conversion element 10, by making the average crystal grain size of the plurality of metal crystal grains (hereinafter, simply called an average crystal grain size) included in the metal layers 28 n and 28 p greater than the thickness of the metal layers 28 n and 28 p, it is possible to improve the element characteristics. Hereinafter, this will be described. In addition, after performing the heat treatment or the like and growing the metal crystal grain having the desired size, on the electrodes 22 n and the electrode 22 p, further, in a case where the conductive film is formed, the relationship between the metal layer in which the metal crystal grain having the desired size is formed, and the thickness of the metal layer, may satisfy the above-described conditions.

The average crystal grain size is obtained by analyzing the front surfaces of the metal layers 28 n and 28 p by an electron backscatter diffraction pattern. The metal layers 28 n and 28 p include the plurality of metal crystal grains.

The average crystal grain size is an average of a product of the crystal grain size of each metal crystal grain and an area occupying ratio. The crystal grain size is obtained by the following equation (1). Crystal grain size=2×{(area of crystal grain)/π}^(1/2)  (1)

The “area of crystal grain” in the equation (1) is measured by using the electron backscatter diffraction pattern. The equation (1) assumes that the calculation is performed on the assumption that the area of the crystal grain is an area of a circle, and on the assumption that the crystal grain size is the diameter of the circle. When obtaining the crystal grain size, a corresponding grain boundary of sigma 3 (Σ3) is not handled as a grain boundary. In addition, in a case where deviation of the crystal orientation is equal to or less than 5 degrees, the same crystal grain is achieved.

The area occupying ratio is obtained by dividing the area of the metal crystal grain by the area of the measurement region. Here, the area of the metal crystal grain is the area when orthographic projection is performed on a plane perpendicular to the thickness direction of the silicon substrate 12. The measurement region is 8 μm×23 μm. Furthermore, the metal crystal grain including the boundary of the measurement region is not included in the calculation of the average crystal grain size.

In a case of being viewed from the thickness direction of the silicon substrate 12, the crystal orientation of the metal crystal grain is preferentially orientated to <111>. In this case, since the crystal orientation of the metal crystal grain is aligned, uniformity of a work function of the metal crystal grain on the interface between the transparent conductive layer 26 n and the metal layer 28 n, and a work function of the metal crystal grain on the interface between the transparent conductive layer 26 p and the metal layer 28 p, is improved. As a result, it is possible to suppress irregularity of the contact resistance. In addition, work functions of a {110} surface, a {100} surface, and a {111} surface of silver, are respectively 4.52 eV, 4.64 eV, and 4.74 eV. The work function of the {111} surface is the largest. Therefore, by making the surface orientation of the metal crystal grain preferentially oriented to {111}, that is, by making the crystal orientation of the metal crystal grain preferentially oriented to <111> with respect to the thickness direction of the silicon substrate 12, in particular, an effect of reducing the contact resistance between the p-type non-crystalline silicon layer 20 p and the electrode 22 p, is achieved.

In a case where a metal film 21 n is heat-treated at 150° C. for 15 minutes, a ratio of occupying the metal layer 28 n by the metal crystal grain having the crystal orientation of the <111> direction within 10 degrees with respect to the thickness direction of the silicon substrate 12, is 49.2%. In a case where a metal film 21 p is heat-treated at 150° C. for 15 minutes, a ratio of occupying the metal layer 28 p by the metal crystal grain having the crystal orientation of the <111> direction within 10 degrees with respect to the thickness direction of the silicon substrate 12, is 48.8%.

In a case where the film thickness of the metal layer 28 n is 0.4 μm, in the plurality of metal crystal grains, a ratio of occupying the metal layer 28 n by the metal crystal grain having the diameter which is equal to or greater than 0.4 μm, is 7.6% before the heat treatment, and is 53.0% after the heat treatment at 150° C. for 15 minutes. In a case where the film thickness of the metal layer 28 p is 0.4 μm, in the plurality of metal crystal grains, a ratio of occupying the metal layer 28 p by the metal crystal grain having the diameter which is equal to or greater than 0.4 μm, is 3.0% before the heat treatment, and is 46.1% after the heat treatment at 150° C. for 15 minutes.

The average crystal grain size depends on the temperature (hereinafter, simply referred to as annealing temperature) when the metal layers 21 n and 21 p are heat-treated. FIG. 3 is a graph illustrating a relationship between the average crystal grain size and the annealing temperature. FIG. 3 illustrates the average crystal grain size in a case where the annealing temperature is 25° C. This shows the average crystal grain size in a state where the heat treatment is not performed. As illustrated in FIG. 3, in the metal layers 28 n and 28 p, when the annealing temperature becomes high, the average crystal grain size becomes large. Here, the thickness of the metal layers 28 n and 28 p is 0.4 μm. In other words, by performing the heat treatment with respect to the metal layers 21 n and 21 p, the average crystal grain size becomes greater than the thickness of the metal layers 28 n and 28 p.

FIG. 4 is a graph illustrating a relationship between the average crystal grain size and the contact resistance.

The contact resistance is measured by creating a sample 30 illustrated in FIG. 5 and using the sample 30. The sample 30 includes a silicon substrate 32, an electrode 34, a non-crystalline silicon layer 36, and an electrode 38.

In the contact resistance between the electrode 22 n and the n-type non-crystalline silicon layer 20 n, the electrode 34 is considered as the electrode 22 n. In this case, the non-crystalline silicon layer 36 contains n-type impurities, and the silicon substrate 32 is an n-type silicon substrate. A resistance ratio of the n-type silicon substrate is equal to or less than 0.01 Ω·cm. The configuration and thickness of the electrode 34 are the same as the configuration and the thickness of the electrode 22 n. The thickness and an impurities concentration of the non-crystalline silicon layer 36 are the same as those of the n-type non-crystalline silicon layer 20 n. The thickness of the silicon substrate 32 is 300 μm.

In the contact resistance between the electrode 22 p and the p-type non-crystalline silicon layer 20 p, the electrode 34 is considered as the electrode 22 p. In this case, the non-crystalline silicon layer 36 contains p-type impurities, and the silicon substrate 32 is a p-type silicon substrate. A resistance ratio of the p-type silicon substrate is equal to or less than 0.01 Ω·cm. The configuration and thickness of the electrode 34 are the same as the configuration and the thickness of the electrode 22 p. The thickness and an impurities concentration of the non-crystalline silicon layer 36 are the same as those of the p-type non-crystalline silicon layer 20 p.

In any case where the contact resistance between the electrode 22 n and the n-type non-crystalline silicon layer 20 n is measured, and where the contact resistance between the electrode 22 p and the p-type non-crystalline silicon layer 20 p is measured, the electrode 38 is a layered structure of titanium (Ti), palladium (Pd), and silver (Ag).

As illustrated in FIG. 4, when the average crystal grain size in the metal layer 28 n becomes greater than the thickness (0.4 μm) of the metal layer 28 n, the contact resistance between the n-type non-crystalline silicon layer 20 n and the electrode 22 n becomes lower than the contact resistance in a state where the heat treatment is not performed. In addition, when the average crystal grain size in the metal layer 28 n is equal to or greater than the 1.33 μm, the contact resistance between the n-type non-crystalline silicon layer 20 n and the electrode 22 n becomes greater than the contact resistance in a state where the heat treatment is not performed (when the average crystal grain size in the metal layer 28 n is equal to or less than 1.14 μm, the contact resistance between the n-type non-crystalline silicon layer 20 n and the electrode 22 n is smaller than the contact resistance in a state where the heat treatment is not performed). Therefore, it is preferable that the average crystal grain size of the metal layer 28 n is greater than 1 times the film thickness of the metal layer 28 n. The average crystal grain size of the metal layer 28 n is more preferably greater than 1 times and less than 3.33 times the film thickness of the metal layer 28 n, still more preferably greater than 1 times and equal to or less than 2.85 times the film thickness of the metal layer 28 n, and further still more preferably equal to or greater than 1.55 times and equal to or less than 2.85 times the film thickness of the metal layer 28 n. Specifically, in a case where the thickness of the metal layer 28 n is 0.4 μm, the average crystal grain size in the metal layer 28 n is preferably greater than 0.4 μm, more preferably greater than 0.4 μm and less than 1.33 μm, still more preferably greater than 0.4 μm and equal to or less than 1.14 μm, and still more preferably equal to or greater than 0.62 μm and equal to or less than 1.14 μm. In this case, the contact resistance becomes extremely low, and the element characteristics are improved.

Here, as a reason why the contact resistance decreases by increasing the average crystal grain size, for example, the following reason is considered.

As illustrated in FIG. 6, it is considered that a high density interface level is present in the crystal grain boundary which is the interface between the metal crystal grains 24. In other words, as the crystal grain boundary becomes dense, the influence of the interface level increases.

In a case where the metal crystal grain 24 is small, the interface level increases. Therefore, as illustrated in FIG. 7, a dipole is formed between the interface level (charged to plus) at which an electron is discharged, and an electron carrier (electron accumulation layer) evoked on the front surface of the transparent conductive layer 26 n. As a result, an energy barrier increases, non-ohmic properties are easily achieved, and the contact resistance increases. In addition, in FIG. 7, in order to make it easy to determine the influence of the interface level, it is described that an interface level region is present between the transparent conductive layer 26 n and the metal layer 28 n.

Meanwhile, in a case where the metal crystal grain 24 is large, the crystal grain boundary becomes small. Therefore, the interface level density effectively decreases. In this case, as illustrated in FIG. 8, band bending occurs so that a Fermi level of the transparent conductive layer 26 n and a Fermi level of the metal layer 28 n match each other, and the electron accumulation layer is formed in the transparent conductive layer 26 n. Since the energy barrier between the transparent conductive layer 26 n and the metal layer 28 n is rarely present, the ohmic properties are achieved, and the contact resistance decreases. In a case where the crystal grain size of the metal crystal grain 24 is large, the contact resistance can be reduced. When the average crystal grain size in the metal layer 22 n is greater than the film thickness of the metal layer 22 n, since most of the crystal grain boundary between the metal crystal grains 24 penetrate in the film thickness direction of the metal layer 22 n, the crystal grain boundary density becomes extremely low in the vicinity of the interface with the transparent conductive layer 26 n, and the interface level density becomes extremely low. Therefore, it is preferable that the average crystal grain size in the metal layer 22 n is greater than the film thickness of the metal layer 22 n. Similarly, it is preferable that the average crystal grain size in the metal layer 22 p is greater than the film thickness of the metal layer 22 p.

The reason why the contact resistance becomes high as the average crystal grain size becomes extremely large, is considered as follows, for example. In other words, when the average crystal grain size becomes extremely large, the diffusion speed of oxygen in the metal layer increases. Accordingly, it is considered that the oxygen is likely to infiltrate into the metal layer from the outside, the metal layer is oxidized and the high resistance is achieved, or high resistance is achieved by making the oxygen reach the non-crystalline silicon layer and oxidizing the non-crystalline silicon layer.

In FIG. 4, when the average crystal grain size in the metal layer 28 p becomes greater than 1.48 times (0.59 μm) the thickness of the metal layer 28 p, the contact resistance between the p-type non-crystalline silicon layer 20 p and the metal layer 28 p becomes greater than the contact resistance in a state where the heat treatment is not performed. In other words, in a case where the average crystal grain size in the metal layer 28 p is equal to or greater than 1.03 times and less than 1.48 times (0.41 μm to 0.59 μm) the thickness of the metal layer 28 p, the contact resistance between the p-type non-crystalline silicon layer 20 p and the electrode 22 p becomes smaller than the contact resistance in a state where the heat treatment is not performed.

The reason why the contact resistance decreases in a case where the average crystal grain size in the metal layer 28 p is equal to or greater than 1.03 times and less than 1.48 times (0.41 μm to 0.59 μm) the thickness of the metal layer 28 p, is considered as similar to that in a case of the metal layer 28 n.

FIG. 9 is a graph illustrating a relationship between the contact resistance (cell resistance) per 1 cm² of a photoelectric conversion element, and an average value of the average crystal grain size. The cell resistance is the contact resistance of the photoelectric conversion element 10 when a ratio of the contact area between the electrode 22 n and the n-type non-crystalline silicon layer 20 n, and the contact area between the electrode 22 p and the p-type non-crystalline silicon layer 20 p, is assumed. The average value of the average crystal grain size is an average value of the average crystal grain size in the electrode 22 n and the average crystal grain size in the electrode 22 p. In FIG. 9, each expression in the general example, such as n:p=2:1, n:p=1:1, n:p=1:2, illustrates that ratios of the contact area between the electrode 22 n and of the n-type non-crystalline silicon layer 20 n, and the contact area between the electrode 22 p and the p-type non-crystalline silicon layer 20 p, are respectively 2:1, 1:1, and 1:2.

In a case where the contact area between the electrode 22 n and the n-type non-crystalline silicon layer 20 n is 1, and the contact area between the electrode 22 p and the p-type non-crystalline silicon layer 20 p is N, the cell resistance is obtained by the following equation (2). Cell resistance={(the contact resistance between the electrode 22n and the n-type non-crystalline silicon layer 20n)×(1+N)}+{(the contact resistance between the electrode 22p and the p-type non-crystalline silicon layer 20p)}×(1+N)/N/}  (2)

As illustrated in FIG. 9, in a case where the contact area between the electrode 22 p and the p-type non-crystalline silicon layer 20 p is 1 times or greater than the contact area between the electrode 22 n and the n-type non-crystalline silicon layer 20 n, and the average value of the average crystal grain size is equal to or greater than 0.41 μm and equal to or less than 0.86 μm, the cell resistance becomes lower than the cell resistance in a state where the heat treatment is not performed. Therefore, it is preferable that the average of the average crystal grain size is equal to or greater than 1.03 times and equal to or less than 2.15 times the thickness of the metal layer 28 n and the thickness of the metal layer 29 n.

FIG. 10 is a graph illustrating a relationship between conversion efficiency η and the average value of the average crystal grain size. The conversion efficiency η is standardized by using the conversion efficiency η in a state where the heat treatment is not performed as a standard. The average value of the average crystal grain size is a value obtained by averaging the average crystal grain size of the plurality of metal crystal grains contained in the metal layer 28 n, and the average crystal grain size of the plurality of metal crystal grains contained in the metal layer 28 p.

FIG. 11 is a graph illustrating a relationship between a curve factor FF and the average value of the average crystal grain size. The curve factor FF is standardized by using the curve factor FF in a state where the heat treatment is not performed as a standard. The average value of the average crystal grain size is obtained by averaging the average crystal grain size of the plurality of metal crystal grains contained in the metal layer 28 n, and the average crystal grain size of the plurality of metal crystal grains contained in the metal layer 28 p.

FIGS. 10 and 11 illustrate a measurement result in a case where the thickness of the metal layers 28 n and 28 p is 0.4 μm, and the contact area between the electrode 22 p and the p-type non-crystalline silicon layer 20 p is 3 times the contact area between the electrode 22 n and the n-type non-crystalline silicon layer 20 n. As illustrated in FIGS. 10 and 11, in a case where the average value of the average crystal grain size is greater than the thickness of the metal layers 28 n and 28 p, the element characteristics (specifically, the conversion efficiency η and the curve factor FF) are improved. In particular, the curve factor FF is improved because the contact resistance between the n-type non-crystalline silicon layer 20 n and the electrode 22 n and the contact resistance between the p-type non-crystalline silicon layer 20 p and the electrode 22 p become low by performing the heat treatment. In other words, in the photoelectric conversion element 10, since the contact resistance between the n-type non-crystalline silicon layer 20 n and the electrode 22 n and the contact resistance between the p-type non-crystalline silicon layer 20 p and the electrode 22 p can become low, it is possible to improve the curve factor FF. As a result, it is possible to improve the conversion efficiency η.

The average value of the average crystal grain size is preferably greater than the thickness of the metal layers 28 n and 28 p and equal to or less than 3.3 times the thickness of the metal layers 28 n and 28 p. The average value of the average crystal grain size is further preferably equal to or greater than 1.03 times the thickness of the metal layers 28 n and 28 p and equal to or less than 3.3 times the thickness of the metal layers 28 n and 28 p. Specifically, in a case where the thickness of the metal layers 28 n and 28 p is 0.4 μm, the average value of the average crystal grain size is preferably equal to or greater than 0.41 μm and equal to or less than 1.32 μm. In this case, as illustrated in FIGS. 10 and 11, the element characteristics are improved.

The average value of the average crystal grain size is more preferably equal to or greater than 1.03 times the thickness of the metal layers 28 n and 28 p, and equal to or less than 2.95 times the thickness of the metal layers 28 n and 28 p. Specifically, in a case where the thickness of the metal layers 28 n and 28 p is 0.4 μm, the average value of the average crystal grain size is equal to or greater than 0.41 μm and equal to or less than the 1.18 μm. In this case, as illustrated in FIGS. 10 and 11, the element characteristics are further improved.

The average value of the average crystal grain size is further more preferably equal to or greater than 1.53 times the thickness of the metal layers 28 n and 28 p, and equal to or less than 2.15 times the thickness of the electrodes 22 n and 22 p. Specifically, in a case where the thickness of the metal layers 28 n and 28 p is 0.4 μm, the average value of the average crystal grain size is more preferably equal to or greater than 0.61 μm and equal to or less than the 0.86 μm. In this case, as illustrated in FIGS. 10 and 11, the element characteristics are still further improved.

Application Examples 1 to 3 of First Embodiment

The photoelectric conversion element according to the first embodiment of the present invention may have configurations illustrated in FIGS. 12 to 14.

FIG. 12 is a sectional view illustrating an example of a schematic configuration of a photoelectric conversion element 10A according to an application example 1 of the first embodiment of the present invention. As illustrated in 12, the photoelectric conversion element 10A is not provided with the intrinsic non-crystalline silicon layer 18 compared to the photoelectric conversion element 10.

When manufacturing the photoelectric conversion element 10A, for example, the intrinsic non-crystalline silicon layer and the p-type non-crystalline silicon layer are formed in order on the rear surface of the silicon substrate 12. Next, in the p-type non-crystalline silicon layer, a part except the part which becomes the p-type non-crystalline silicon layer 20 p later is removed, and in the intrinsic non-crystalline silicon layer, a part except the part which becomes the intrinsic non-crystalline silicon layer 19 later is removed. Next, on the resist pattern formed on the p-type non-crystalline silicon layer 20 p, and on the rear surface of the silicon substrate 12, the n-type non-crystalline silicon layer is formed. Next, the resist pattern formed on the p-type non-crystalline silicon layer 20 p is removed. Accordingly, on the rear surface of the silicon substrate 12, the intrinsic non-crystalline silicon layer 19, the p-type non-crystalline silicon layer 20 p, and the n-type non-crystalline silicon layer 20 n are formed.

FIG. 13 is a sectional view illustrating an example of a schematic configuration of a photoelectric conversion element 10B according to an application example 2 of the first embodiment of the present invention. As illustrated in FIG. 13, the photoelectric conversion element 10B is not provided with the intrinsic non-crystalline silicon layer 19 compared to the photoelectric conversion element 10.

When manufacturing the photoelectric conversion element 10B, for example, the intrinsic non-crystalline silicon layer, the n-type non-crystalline silicon layer, and the coating layer are formed in order on the rear surface of the silicon substrate 12. Next, by using the photolithography method, the coating layer, the n-type non-crystalline silicon layer, and the intrinsic non-crystalline silicon layer are patterned, a part of the silicon substrate 12 is exposed, and the n-type non-crystalline silicon layer 20 n and the intrinsic non-crystalline silicon layer 18 are formed. At this time, the coating layer is formed on the n-type non-crystalline silicon layer 20 n. Next, on the coating layer formed on the n-type non-crystalline silicon layer 20 n, and on the rear surface of the silicon substrate 12, the p-type non-crystalline silicon layer is formed. Next, the coating layer formed on the n-type non-crystalline silicon layer 20 n is removed. Accordingly, on the rear surface of the silicon substrate 12, the intrinsic non-crystalline silicon layer 18 and the p-type non-crystalline silicon layer 20 p are formed, and the n-type non-crystalline silicon layer 20 n is formed on the intrinsic non-crystalline silicon layer 18.

In addition, FIG. 14 is a sectional view illustrating an example of a schematic configuration of a photoelectric conversion element 10C according to an application example 3 of the first embodiment of the present invention. As illustrated in FIG. 14, the photoelectric conversion element 10C is not provided with the intrinsic non-crystalline silicon layers 18 and 19 compared to the photoelectric conversion element 10.

When manufacturing the photoelectric conversion element 10C, for example, the n-type silicon layer and the coating layer are formed in order on the rear surface of the silicon substrate 12. Next, the coating layer and the n-type non-crystalline silicon layer are patterned, a part of the silicon substrate 12 is exposed, and the n-type non-crystalline silicon layer 20 n is formed. At this time, the coating layer is formed on the n-type non-crystalline silicon layer 20 n. Next, on the coating layer formed on the n-type non-crystalline silicon layer 20 n, and on the rear surface of the silicon substrate 12, the p-type non-crystalline silicon layer is formed. Next, the coating layer formed on the n-type non-crystalline silicon layer 20 n is removed. Accordingly, on the rear surface of the silicon substrate 12, the n-type non-crystalline silicon layer 20 n and the p-type non-crystalline silicon layer 20 p are formed.

Second Embodiment

FIG. 15 is a sectional view illustrating a configuration of a photoelectric conversion element 50 according to a second embodiment of the present invention. The photoelectric conversion element 50 includes a silicon substrate 52, a non-crystalline film 54, a non-crystalline film 56, an electrode 58, an insulation film 60, and an electrode 62.

The silicon substrate 52 is an n-type single crystal silicon substrate. The silicon substrate 52 includes a p-type diffusion layer 64 p and an n-type diffusion layer 64 n.

The p-type diffusion layer 64 p contains, for example, boron (B) as p-type impurities. The maximum concentration of boron (B) is, for example, 1×10¹⁸ cm⁻³ to 1×10²⁰ cm⁻³. The thickness of the p-type diffusion layer 64 p is, for example, 50 nm to 1000 nm.

The n-type diffusion layer 64 n is in contact with the rear surface opposite to the light incident side of the silicon substrate 52, and is disposed at a desired interval in the in-surface direction of the silicon substrate 52. The n-type diffusion layer 64 n contains, for example, phosphorus (P) as n-type impurities. The maximum concentration of phosphorus (P) is, for example, 1×10¹⁸ cm⁻³ to 1×10²⁰ cm⁻³. The thickness of the n-type diffusion layer 64 n is, for example, 50 nm to 1000 nm.

Other description of the silicon substrate 52 is the same as the description of the silicon substrate 12.

The non-crystalline film 54 is disposed to be in contact with the front surface on the light-incident side of the silicon substrate 52. The non-crystalline film 54 includes at least the non-crystalline phase, and made of, for example, a-Si:H. The thickness of the non-crystalline film 54 is, for example, 1 nm to 20 nm.

The non-crystalline film 56 is disposed to be in contact with the non-crystalline film 54. The non-crystalline film 54 includes at least the non-crystalline phase, and made of, for example, silicon nitride. The thickness of the non-crystalline film 56 is, for example, 50 nm to 200 nm.

The electrode 58 penetrates the non-crystalline film 54 and the non-crystalline film 56, is in contact with the p-type diffusion layer 64 p of the silicon substrate 52, and is disposed on the non-crystalline film 56. The electrode 58 includes a transparent conductive layer 58A and a metal layer 58B. The transparent conductive layer 58A is in contact with the p-type diffusion layer 64 p. The transparent conductive layer 58A is made of, for example, ITO. The thickness of the transparent conductive layer 58A is, for example, 0.1 nm to 20 nm. The metal layer 58B is in contact with the transparent conductive layer 58A. The metal layer 58B has silver as a main component. The metal layer 58B may contain metal other than silver. The thickness of the metal layer 58B is, for example, 100 nm to 1000 nm.

The insulation film 60 is disposed to be in contact with the rear surface of the silicon substrate 52. The insulation film 60 is made of, for example, silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxide. The thickness of the insulation film 60 is, for example, 50 nm to 1000 nm.

The electrode 62 penetrates the insulation film 60, is in contact with the n-type diffusion layer 64 n of the silicon substrate 52, and is disposed to cover the insulation film 60. The electrode 62 includes a transparent conductive layer 62A and a metal layer 62B. The transparent conductive layer 62A is in contact with the n-type diffusion layer 64 n. The transparent conductive layer 62A is made of, for example, ITO. The thickness of the transparent conductive layer 62A is, for example, 0.1 nm to 20 nm. The metal layer 62B is in contact with the transparent conductive layer 62A. The metal layer 62B has silver as a main component. The metal layer 62B may contain metal other than silver. The thickness of the metal layer 62B is, for example, 100 nm to 1000 nm.

[Manufacturing Method of Photoelectric Conversion Element]

With reference to FIGS. 16A to 16G, a manufacturing method of the photoelectric conversion element 50 will be described.

First, as illustrated in FIG. 16A, the n-type diffusion layer 64 n is formed on the silicon substrate 52. Specifically, first, the silicon substrate 52 is prepared. Next, the rear surface of the silicon substrate 52 is coated with the resist. Next, the resist is patterned by the photolithography method, and the resist pattern is formed. Next, by using the resist pattern as a mask, the n-type impurities, such as P and arsenic (As), are ion-injected into the silicon substrate 52. According to this, the n-type diffusion layer 64 n is formed on the rear surface side of the silicon substrate 52. In addition, after the ion injection, the heat treatment may be performed for electrically vitalizing the n-type impurities. Instead of the ion injection method, a gas phase diffusion method, a solid phase diffusion method, a plasma doping method, or an ion doping method, may be used.

Next, as illustrated in FIG. 16B, the insulation film 60 is formed on the entire rear surface of the silicon substrate 52. The insulation film 60 is formed, for example, by the plasma CVD method. In addition, the insulation film 60 may be formed by an atomic layer deposition method (ALD) and a heat CVD method.

Next, as illustrated in FIG. 16C, the p-type diffusion layer 64 p is formed on the silicon substrate 52. Specifically, the p-type impurities, such as B, gallium (Ga), or indium (In), are ion-injected into the silicon substrate 52 from the light-incident side. Accordingly, the p-type diffusion layer 64 p is formed on the light-incident side of the silicon substrate 52. In addition, after the ion injection, the heat treatment may be performed for electrically vitalizing the p-type impurities. In addition, not being limited to the ion injection, the p-type diffusion layer 64 p may be formed by a gas phase diffusion method and a solid phase diffusion method. Instead of the ion injection method, a gas phase diffusion method, a solid phase diffusion method, a plasma doping method, or an ion doping method, may be used.

Next, as illustrated in FIG. 16D, the non-crystalline film 54 is formed on the light-receiving surface of the silicon substrate 52. The non-crystalline film 54 is formed, for example, by the plasma CVD.

Next, as illustrated in FIG. 16E, the non-crystalline film 56 is formed on the non-crystalline film 54. The non-crystalline film 56 is formed, for example, by the plasma CVD.

Next, as illustrated in FIG. 16F, the transparent conductive layers 58A and 62A and metal layers 581B and 621B, are formed. A forming method of the transparent conductive layers 58A and 62A and the metal layers 581B and 621B is, for example, as follows.

First, the entire surface of the non-crystalline film 56 is coated with the resist. Next, the resist is patterned by the photolithography method, and the resist pattern is formed. Next, by using mixed liquid of hydrofluoric acid and nitric acid by using a photoresist as a mask, etching is performed with respect to a part of the non-crystalline film 56 and the non-crystalline film 54. Next, resist pattern is removed. Accordingly, a part of the p-type diffusion layer 64 p is exposed. Next, by the deposition method and the sputtering method, the transparent conductive layer and the metal layer are formed. Next, the transparent conductive layer and the metal layer are patterned. Accordingly, the transparent conductive layer 58A and the metal layer 581B are formed.

Next, the entire surface of the insulation film 60 is coated with the resist. Next, the resist is patterned by the photolithography method, and the resist pattern is formed. Next, by using the resist pattern as a mask, by using hydrofluoric acid, the etching is performed with respect to a part of the insulation film 60, and the resist pattern is removed. Accordingly, a part of the n-type diffusion layer 64 n of the silicon substrate 52 is exposed.

Next, by using the deposition method or the sputtering method, the transparent conductive layer 62A and the metal layer 621B, are formed.

Next, the heat treatment is performed with respect to the metal layers 581B and 621B, and the electrodes 58 and 62 are formed. The heat treatment is performed similar to the first embodiment. Accordingly, as illustrated in FIG. 16G, the photoelectric conversion element 50 is obtained.

Even in the photoelectric conversion element 50, similar to the photoelectric conversion element 10, the element characteristics are improved.

In addition, in the photoelectric conversion element 50, by the p-type diffusion layer 64 p provided on the entire front surface of the silicon substrate 52, the depletion layer is formed on the entire light-receiving surface of the silicon substrate 52, and high carrier transmission in the horizontal direction is achieved by the p-type diffusion layer 64 p. According to this, it is possible to effectively separate electron-positive hole pair generated by the light. Furthermore, by the non-crystalline film 54 (for example, i-type a-Si:H) provided on the front surface of the silicon substrate 52, it is possible to obtain a high passivation effect. In a case where a-Si:H is used as the non-crystalline film 54, the passivation performance deteriorates due to high temperature processing (for example, 300° C. or higher), but in the photoelectric conversion element 50, the low contact resistance is obtained in a low temperature process at 250° C. or lower.

In addition, the photoelectric conversion element 50 may be provided with the n-type diffusion layer instead of the p-type diffusion layer 64 p, and may be provided with the p-type diffusion layer instead of the n-type diffusion layer 64 n. In addition, in the photoelectric conversion element 50, the conductive type of the silicon substrate 52 may be the p-type.

Application Example of Second Embodiment

FIG. 17 is a sectional view illustrating a schematic configuration of a photoelectric conversion element 50A according to an application example of the second embodiment. Compared to the photoelectric conversion element 50, instead of the non-crystalline film 54, the photoelectric conversion element 50A is provided with a non-crystalline film 70 and a non-crystalline film 72. In addition, compared to the photoelectric conversion element 50, the photoelectric conversion element 50A is provided with an electrode 76 instead of the electrode 58.

The non-crystalline film 70 includes at least the non-crystalline phase, and is made of a-Si, for example. It is preferable that the non-crystalline film 70 is made of the i-type a-Si, but may contain p-type impurities having lower concentration than the concentration of the p-type impurities contained in the non-crystalline film 72. The thickness of the non-crystalline film 70 is, for example, 5 nm to 20 nm. The non-crystalline film 70 is in contact with the p-type diffusion layer 64 p of the silicon substrate 50, is disposed on the p-type diffusion layer 64 p, and passivates the silicon substrate 52.

The non-crystalline film 72 includes at least non-crystalline phase, and is made of, for example, p-type a-Si:H. The film thickness of the non-crystalline film 72 is, for example, 1 nm to 30 nm. The non-crystalline film 72 is in contact with the non-crystalline film 70, and is disposed on the non-crystalline film 70.

The electrode 76 penetrates the non-crystalline film 56, is in contact with the non-crystalline film 72, and is disposed on the non-crystalline film 56. The electrode 76 includes a transparent conductive layer 76A and a metal layer 76B. The transparent conductive layer 76A is in contact with the non-crystalline film 72. The transparent conductive layer 76A is made of, for example, ITO. The thickness of the transparent conductive layer 76A is, for example, 0.1 nm to 20 nm. The metal layer 76B is in contact with the transparent conductive layer 76A. The metal layer 76B has silver as a main component. The metal layer 76B may contain metal other than silver. The thickness of the metal layer 76B is, for example, 100 nm to 1000 nm.

In the photoelectric conversion element 50A, the electrode 76 is not directly in contact with the silicon substrate 52, and the front surface of the silicon substrate 52 is coated with the non-crystalline film 70. Therefore, compared to the photoelectric conversion element 50, more excellent passivation characteristics are further obtained. As a result, the photoelectric conversion efficiency can be further improved.

A manufacturing method of the photoelectric conversion element 50A may be a method in which a process of forming the non-crystalline film 54 is changed to a process of forming the non-crystalline film 70 and the non-crystalline film 72, and in which a process of forming the electrode 58 is changed to a process of forming the electrode 76, from the manufacturing method of the photoelectric conversion element 50.

In addition, the photoelectric conversion element 50A may not be provided with the non-crystalline film 70. In the photoelectric conversion element 50A, the n-type diffusion layer may be provided instead of the p-type diffusion layer 64 p, the p-type diffusion layer may be provided instead of the n-type diffusion layer 64 n, and the film made of n-type a-Si:H may be provided instead of the non-crystalline film 72. The conductive type of the silicon substrate 52 may be changed to the p-type.

Third Embodiment

FIG. 18 is a sectional view illustrating a schematic configuration of a photoelectric conversion element 80 according to a third embodiment of the present invention. In the photoelectric conversion element 80, a silicon substrate 82 is provided instead of the silicon substrate 52 of the photoelectric conversion element 50, non-crystalline films 84 and 86 are provided instead of the insulation film 60, and an electrode 88 is provided instead of the electrode 62. Other parts are the same as those of the photoelectric conversion element 50.

In the silicon substrate 82, an n-type diffusion layer 90 n is provided instead of the n-type diffusion layer 64 n of the silicon substrate 52. Other parts are the same as those of the silicon substrate 52.

The n-type diffusion layer 90 n is in contact with the entire rear surface opposite to the light-incident side of the silicon substrate 82, and is disposed in the silicon substrate 82. The n-type diffusion layer 90 n has the same thickness as that of the n-type diffusion layer 64 n, and contains the n-type impurities having the same concentration as that of the n-type impurities of the n-type diffusion layer 64 n.

The non-crystalline thin film 84 includes at least the non-crystalline phase, and is made of, for example, i-type a-Si:H or n-type a-Si:H. In addition, the film thickness of the non-crystalline thin film 84 is, for example, 1 nm to 20 nm. The non-crystalline thin film 84 is in contact with the rear surface opposite to the light-incident side of the silicon substrate 82, and is disposed on the silicon substrate 82.

The non-crystalline thin film 86 includes at least the non-crystalline phase, and is made of, for example, silicon nitride. In addition, the film thickness of the non-crystalline thin film 86 is, for example, 50 nm to 200 nm.

The electrode 88 penetrates the non-crystalline thin films 84 and 86, is in contact with the n-type diffusion layer 90 n, and is disposed on the non-crystalline thin film 86. The electrode 88 includes a transparent conductive layer 88A and a metal layer 88B. The transparent conductive layer 88A is in contact with the n-type diffusion layer 90 n. The transparent conductive layer 88A is made of, for example, ITO. The thickness of the transparent conductive layer 88A is, for example, 0.1 nm to 20 nm. The metal layer 88B is in contact with the transparent conductive layer 88A. The metal layer 88B has silver as a main component. The metal layer 88B may contain metal other than silver. The thickness of the metal layer 88B is, for example, 100 nm to 1000 nm.

In the photoelectric conversion element 80, the front surface on the light-incident side of the silicon substrate 82 is passivated by the non-crystalline thin film 54, and the rear surface of the silicon substrate 82 is passivated by the non-crystalline thin film 84. Accordingly, high photoelectric conversion efficiency is obtained. Furthermore, the light may be incident on the rear surface side of the silicon substrate 82.

[Manufacturing Method of Photoelectric Conversion Element]

With reference to FIGS. 19A to 19F, a manufacturing method of the photoelectric conversion element 80 will be described.

First, as illustrated in FIG. 19A, the n-type diffusion layer 90 n is formed on the silicon substrate 82. Specifically, n-type impurities, such as P and arsenic (As), are ion-injected into the silicon substrate 82, and the n-type diffusion layer 90 n is formed on the rear surface side of the silicon substrate 82. In addition, after the ion injection, the heat treatment may be performed for electrically vitalizing the n-type impurities. Instead of the ion injection method, a gas phase diffusion method, a solid phase diffusion method, a plasma doping method, or an ion doping method, may be used.

Next, as illustrated in FIG. 19B, the p-type diffusion layer 64 p is formed on the silicon substrate 82. Specifically, p-type impurities, such as B, gallium (Ga), or indium (In), are ion-injected into the silicon substrate 82 from the light-incident side. Accordingly, the p-type diffusion layer 64 p is formed on the light-incident side of the silicon substrate 82. In addition, after the ion injection, the heat treatment may be performed for electrically vitalizing the p-type impurities. In addition, not being limited to the ion injection, the p-type diffusion layer 64 p may be formed by a gas phase diffusion method and a solid phase diffusion method.

Next, as illustrated in FIG. 19C, the non-crystalline films 54 and 56 are formed on the light-receiving surface of the silicon substrate 82. The non-crystalline films 54 and 56 are formed, for example, by the plasma CVD.

Next, as illustrated in FIG. 19D, the non-crystalline thin films 84 and 86 are layered in order on the rear surface of the silicon substrate 82. The non-crystalline films 84 and 86 are formed, for example, by the plasma CVD.

Next, as illustrated in FIG. 19E, the transparent conductive layers 58A and 88A and the metal layers 581B and 881B are formed. A forming method of the transparent conductive layers 58A and 88A and the metal layers 581B and 881B is, for example, as follows.

First, the entire surface of the non-crystalline film 56 is coated with the resist. Next, the resist is patterned by the photolithography method, and the resist pattern is formed. Next, by using a photoresist as a mask, etching is performed with respect to a part of the non-crystalline film 56 and the non-crystalline film 54. Next, resist pattern is removed. Accordingly, a part of the p-type diffusion layer 64 p is exposed. Next, by the deposition method and the sputtering method, the transparent conductive layer and the metal layer are formed. Next, the transparent conductive layer and the metal layer are patterned. Accordingly, the transparent conductive layer 58A and the metal layer 581B are formed.

Next, the entire surface of the non-crystalline film 86 is coated with the resist. Next, the resist is patterned by the photolithography method, and the resist pattern is formed. Next, by using the resist pattern as a mask, the etching is performed with respect to a part of the non-crystalline film 86, and the resist pattern is removed. Accordingly, a part of n-type diffusion layer 64 n of the silicon substrate 82 is exposed.

Next, by using the deposition method and the sputtering method, the transparent conductive layer and the metal layer are formed. Next, the transparent conductive layer and the metal layer are patterned. Accordingly, the transparent conductive layer 88A and the metal layer 881B are formed.

Next, the heat treatment is performed with respect to the metal layers 581B and 881B, and the electrodes 58 and 88 are formed. The heat treatment is performed similar to the first embodiment. Accordingly, as illustrated in FIG. 19F, the photoelectric conversion element 80 is obtained.

In the photoelectric conversion element 80, similar to the photoelectric conversion element 10, the element characteristics are improved.

In addition, in the photoelectric conversion element 80, the n-type diffusion layer may be provided instead of the p-type diffusion layer 64 p, and the p-type diffusion layer may be provided instead of the n-type diffusion layer 90 n. In this case, the non-crystalline thin film 54 is made of i-type a-Si:H or n-type a-Si:H, and the non-crystalline thin film 84 is made of i-type a-Si:H or p-type a-Si:H.

Application Example 1 of Third Embodiment

FIG. 20 is a vertically sectional view illustrating a schematic configuration of a photoelectric conversion element 80A according to an application example 1 of the third embodiment. Compared to the photoelectric conversion element 80, the photoelectric conversion element 80A is provided with the non-crystalline film 70 and the non-crystalline film 72 instead of the non-crystalline film 54. Instead of the non-crystalline film 84, a non-crystalline film 94 and a non-crystalline film 96 are provided. Instead of the electrode 58, the electrode 76 is provided. Instead of the electrode 88, an electrode 98 is provided.

The non-crystalline thin film 94 includes at least the non-crystalline phase, and is made of, for example, i-type a-Si:H or n-type a-Si:H. The non-crystalline thin film 94 is in contact with the rear surface of the silicon substrate 82, and is disposed on the rear surface of the silicon substrate 82.

The non-crystalline thin film 96 includes at least the non-crystalline phase, and is made of, for example, n-type a-Si. The non-crystalline thin film 96 is in contact with the non-crystalline film 94, and is disposed on non-crystalline thin film 941.

The electrode 98 penetrates the non-crystalline thin film 86, is in contact with the non-crystalline thin film 96, and is disposed on the non-crystalline thin film 86. The electrode 98 includes a transparent conductive layer 98A and a metal layer 98B. The transparent conductive layer 98A is in contact with the non-crystalline film 96. The transparent conductive layer 98A is made of, for example, ITO. The thickness of the transparent conductive layer 98A is, for example, 0.1 nm to 20 nm. The metal layer 98B is in contact with the transparent conductive layer 98A. The metal layer 98B has silver as a main component. The metal layer 98B may contain metal other than silver. The thickness of the metal layer 98B is, for example, 100 nm to 1000 nm.

A manufacturing method of the photoelectric conversion element 80A may be a method in which a process of forming the non-crystalline film 54 is changed to a process of forming the non-crystalline film 70 and the non-crystalline film 72, a process of forming the non-crystalline film 84 is changed to a process of forming the non-crystalline film 94 and the non-crystalline film 96, a process of forming the electrode 58 is changed to a process of forming the electrode 76, and a process of forming the electrode 88 is changed to a process of forming the electrode 98, from the manufacturing method of the photoelectric conversion element 80.

In the configurations of the photoelectric conversion element 80A, the non-crystalline films 70 and 72 are formed between the electrode 76 and the silicon substrate 82, and the non-crystalline films 94 and 96 are formed between the electrode 98 and the silicon substrate 82. Therefore, compared to the photoelectric conversion element 80, a higher passivation effect is obtained.

In addition, the photoelectric conversion element 80A may not be provided with the non-crystalline films 70 and 94. In the photoelectric conversion element 80A, the n-type diffusion layer may be provided instead of the p-type diffusion layer 64 p, the p-type diffusion layer may be provided instead of the n-type diffusion layer 90 n, a film made of n-type a-Si:H may be provided instead of the non-crystalline film 72, and a film made of p-type a-Si:H may be provided instead of the non-crystalline film 96. The conductive type of the silicon substrate 82 may be changed to the p-type.

Application Example 2 of Third Embodiment

FIG. 21 is a vertically sectional view illustrating a schematic configuration of a photoelectric conversion element 80B according to an application example 2 of the third embodiment. Compared to the photoelectric conversion element 80, instead of the non-crystalline film 54, the photoelectric conversion element 80B is provided with the non-crystalline film 70 and the non-crystalline film 72. Instead of the electrode 58, the electrode 76 is provided.

A manufacturing method of the photoelectric conversion element 80B may be a method in which a process of forming the non-crystalline film 54 is changed to a process of forming the non-crystalline film 70 and the non-crystalline film 72, and a process of forming the electrode 58 is changed to a process of forming the electrode 76, from the manufacturing method of the photoelectric conversion element 80.

In addition, the photoelectric conversion element 80B may not be provided with the non-crystalline film 70. In the photoelectric conversion element 80B, the n-type diffusion layer may be provided instead of the p-type diffusion layer 64 p, the p-type diffusion layer may be provided instead of the n-type diffusion layer 90 n, and a film made of n-type a-Si:H may be provided instead of the non-crystalline film 72. The conductive type of the silicon substrate 82 may be changed to the p-type.

Fourth Embodiment

FIG. 22 is a schematic view illustrating a configuration of the photoelectric conversion module provided with the photoelectric conversion element according to the embodiment. With reference to FIG. 22, a photoelectric conversion module 1000 includes a plurality of photoelectric conversion elements 1001, a cover 1002, output terminals 1003 and 1004.

The plurality of photoelectric conversion elements 1001 are disposed in a shape of an array, and are connected to each other in series. Instead of being connected to each other in series, parallel connection or connection in which the series connection and the parallel connection are combined, may be employed. Each of the plurality of photoelectric conversion elements 1001 is made of any of the photoelectric conversion elements 10, 10A, 10B, 10C, 50, 50A, 80, 80A, and 80B.

The cover 1002 is made of pollution-resistant cover, and covers the plurality of photoelectric conversion elements 1001.

The output terminal 1003 is connected to the photoelectric conversion element 1001 disposed at one end among the plurality of photoelectric conversion elements 1001 that are connected to each other in series.

The output terminal 1004 is connected to the photoelectric conversion element 1001 disposed at the other end among the plurality of photoelectric conversion elements 1001 that are connected to each other in series.

As described above, the characteristics of the photoelectric conversion elements 10, 10A, 10B, 10C, 50, 50A, 80, 80A, and 80B, are improved. Therefore, the performance of the photoelectric conversion module 1000 can be improved.

In addition, not being limited to the configuration illustrated in FIG. 22, the photoelectric conversion module according to the fourth embodiment may be configured in any manner as long as any of the photoelectric conversion elements 10, 10A, 10B, 10C, 50, 50A, 80, 80A, and 80B, is used.

Fifth Embodiment

FIG. 23 is a schematic view illustrating a configuration of a solar photovoltaic power generation system provided with the photoelectric conversion element according to the embodiment. With reference to FIG. 23, a solar photovoltaic power generation system 1100 includes a photoelectric conversion module array 1101, a connection box 1102, a power conditioner 1103, a distribution board 1104, and a power meter 1105.

The connection box 1102 is connected to the photoelectric conversion module array 1101. The power conditioner 1103 is connected to the connection box 1102. The distribution board 1104 is connected to the power conditioner 1103 and an electrical machine 1110. The power meter 1105 is connected to the distribution board 1104 and a commercial power system.

The photoelectric conversion module array 1101 converts sunlight into electricity, generates DC power, and supplies the generated DC power to the connection box 1102.

The connection box 1102 receives the DC power generated by the photoelectric conversion module array 1101, and supplies the received DC power to the power conditioner 1103.

The power conditioner 1103 converts the DC power received from the connection box 1102 into AC power, and supplies the converted AC power to the distribution board 1104.

The distribution board 1104 supplies the AC power received from the power conditioner 1103, and/or commercial power received via the power meter 1105, to the electrical machine 1110. In addition, when the AC power received from the power conditioner 1103 is greater than power consumption of the electrical machine 1110, the distribution board 1104 supplies residual AC power to the commercial power system via the power meter 1105.

The power meter 1105 measures the power in the direction toward the distribution board 1104 from the commercial power system, and measures the power in the direction toward the commercial power system from the distribution board 1104.

FIG. 24 is a schematic view illustrating a configuration of the photoelectric conversion module array 1101 illustrated in FIG. 23. With reference to FIG. 24, the photoelectric conversion module array 1101 includes a plurality of photoelectric conversion modules 1120 and output terminals 1121 and 1122.

The plurality of photoelectric conversion modules 1120 are disposed in a shape of an array, and are connected to each other in series. Each of the plurality of photoelectric conversion modules 1120 is made of the photoelectric conversion module 1000 illustrated in FIG. 22.

The output terminal 1121 is connected to the photoelectric conversion module 1120 which is positioned at one end among the plurality of photoelectric conversion modules 1120 that are connected to each other in series.

The output terminal 1122 is connected to the photoelectric conversion module 1120 which is positioned at the other end among the plurality of photoelectric conversion modules 1120 that are connected to each other in series.

An operation in the solar photovoltaic power generation system 1100 will be described. The photoelectric conversion module array 1101 converts the sunlight into electricity, generates the DC power, and supplies the generated DC power to the power conditioner 1103 via the connection box 1102.

The power conditioner 1103 converts the DC power received from the photoelectric conversion module array 1101 into the AC power, and supplies the converted AC power to the distribution board 1104.

When the AC power received from the power conditioner 1103 is equal to or greater than the power consumption of the electrical machine 1110, the distribution board 1104 supplies the AC power received from the power conditioner 1103 to the electrical machine 1110. In addition, the distribution board 1104 supplies the residual AC power to the commercial power system via the power meter 1105.

In addition, when the AC power received from the power conditioner 1103 is less than the power consumption of the electrical machine 1110, the distribution board 1104 supplies the AC power received from the commercial power system and the AC power received from the power conditioner 1103, to the electrical machine 1110.

As described above, the solar photovoltaic power generation system 1100 is provided with any of the photoelectric conversion elements 10, 10A, 10B, 10C, 50, 50A, 80, 80A, and 80B in which the element characteristics are improved. Therefore, performance of the solar photovoltaic power generation system 1100 can be improved.

In addition, not being limited to configurations illustrated in FIGS. 23 and 24, the solar photovoltaic power generation system according to the fifth embodiment may be configured in any manner as long as any of the photoelectric conversion elements 10, 10A, 10B, 10C, 50, 50A, 80, 80A, and 80B is used.

Sixth Embodiment

FIG. 25 is a schematic view illustrating a configuration of the solar photovoltaic power generation system provided with the photoelectric conversion element according to the embodiment. With reference to FIG. 25, a solar photovoltaic power generation system 1200 includes subsystems 1201 to 120 n (n is an integer which is equal to or greater than 2), power conditioners 1211 to 121 n, and a converter 1221. The solar photovoltaic power generation system 1200 is a solar photovoltaic power generation system of which the dimension is greater than that of the solar photovoltaic power generation system 1100 illustrated in FIG. 23.

The power conditioners 1211 to 121 n are respectively connected to the subsystems 1201 to 120 n.

The converter 1221 is connected to the power conditioners 1211 to 121 n and the commercial power system.

Each of the subsystems 1201 to 120 n is made of module systems 1231 to 123 j (j is an integer which is equal to or greater than 2).

Each of the module systems 1231 to 123 j includes photoelectric conversion module arrays 1301 to 130 i (i is an integer which is equal to or greater than 2), connection boxes 1311 to 131 i, and a power collection box 1321.

Each of the photoelectric conversion module arrays 1301 to 130 i is configured the same as the photoelectric conversion module array 1101 illustrated in FIG. 34.

The connection boxes 1311 to 131 i are respectively connected to the photoelectric conversion module arrays 1301 to 130 i.

The power collection box 1321 is connected to the connection boxes 1311 to 131 i. In addition, j power collection boxes 1321 of the subsystem 1201 are connected to the power conditioner 1211. j power collection boxes 1321 of the subsystem 1202 are connected to the power conditioner 1212. Hereinafter, similarly, j power collection boxes 1321 of the subsystem 120 n are connected to the power conditioner 121 n.

i photoelectric conversion module arrays 1301 to 130 i of the module system 1231 convert the sunlight into electricity, generate the DC power, and supply the generated DC power to the power collection box 1321 via each of the connection boxes 1311 to 131 i. i photoelectric conversion module arrays 1301 to 130 i of the 1232 convert the sunlight into electricity, generate the DC power, and supply the generated DC power to the power collection box 1321 via each of the connection boxes 1311 to 131 i. Hereinafter, similarly, i photoelectric conversion module arrays 1301 to 130 i of the module system 123 j convert the sunlight into electricity, generate the DC power, and supply the generated DC power to the power collection box 1321 via the connection boxes 1311 to 131 i.

In addition, j power collection boxes 1321 of the subsystem 1201 supply the DC power to the power conditioner 1211.

j power collection boxes 1321 of the subsystem 1202 similarly supply the DC power to the power conditioner 1212.

Hereinafter, similarly, j power collection boxes 1321 of the subsystem 120 n supply the DC power to the power conditioner 121 n.

The power conditioners 1211 to 121 n respectively convert the DC power received from the subsystems 1201 to 120 n to the AC power, and supply the converted AC power to the converter 1221.

The converter 1221 receives the AC power from the power conditioners 1211 to 121 n, converts a voltage level of the received AC power, and supplies the power to the commercial power system.

As described above, the solar photovoltaic power generation system 1200 is provided with any of the photoelectric conversion elements 10, 10A, 10B, 10C, 50, 50A, 80, 80A, and 80B in which the element characteristics are improved. Therefore, the performance of the solar photovoltaic power generation system 1200 can be improved.

In addition, not being limited to configurations illustrated in FIG. 25, the solar photovoltaic power generation system according to the sixth embodiment may be configured in any manner as long as any of the photoelectric conversion elements 10, 10A, 10B, 10C, 50, 50A, 80, 80A, and 80B is used.

Above, the embodiments of the present invention are described in detail, but the description is merely an example, but the description is merely an example, and the present invention is not limited to the above-described embodiments.

For example, in the first embodiment, the silicon substrate 12 may be the p-type single crystal silicon substrate. In this case, it is preferable that the width dimension of the p-type non-crystalline silicon layer 20 p becomes smaller than the width dimension of the n-type non-crystalline silicon layer 20 n in the in-surface direction of the silicon substrate 12. This is similar in the application examples 1 to 3.

In the first embodiment, the texture structure on the light-receiving surface side of the silicon substrate 12, and the texture structure of the rear surface side, are not necessary configuration elements. This is similar in the application examples 1 to 3.

In the first embodiment, the passivation film 14 and the reflection preventing film 16 are not necessary configuration elements. This is similar in the application examples 1 to 3.

In the first embodiment, the high concentration region may be formed on the light-receiving surface side of the silicon substrate 12. The high concentration region is a region in which the impurities having the same conductive type as the silicon substrate 12 are doped to higher concentration than the silicon substrate 12. The high concentration region functions as a front surface field (FSF). This is similar in the application examples 1 to 3. 

What is claimed is:
 1. A photoelectric conversion element comprising: a semiconductor substrate; a first non-crystalline semiconductor layer having a first conductive type; a second non-crystalline semiconductor layer having a second conductive type opposite to the first conductive type; a first electrode which is in contact with the first non-crystalline semiconductor layer; and a second electrode which is in contact with the second non-crystalline semiconductor layer, wherein the first electrode includes a first transparent conductive layer formed on the first non-crystalline semiconductor layer and a first metal layer formed on the first transparent conductive layer, wherein the first metal layer includes a plurality of metal crystal grains, wherein an average crystal grain size of the plurality of metal crystal grains in an in-surface direction of the first metal layer is greater than 1.5 times a thickness of the first metal layer, wherein the plurality of metal crystal grains includes metal crystal grains oriented in a <110> direction, metal crystal grains oriented in a <100> direction, and metal crystal grains oriented in a <111> direction, wherein each of the <100> direction, the <110> direction, and the <111> direction is within 10 degrees with respect to a thickness direction of the semiconductor substrate, and wherein an area of the plurality of metal crystal grains oriented in the <111> direction is greater than an area of the plurality of metal crystal grains oriented in the <100> direction and an area of the plurality of metal crystal grains oriented in the <110> direction.
 2. The photoelectric conversion element according to claim 1, wherein the first electrode is made of a metal film which has silver as a main component.
 3. The photoelectric conversion element according to claim 1, wherein the first non-crystalline semiconductor layer and the second non-crystalline semiconductor layer are formed on a rear surface opposite to a light-receiving surface on the semiconductor substrate.
 4. The photoelectric conversion element according to claim 1, wherein the first conductive type is an n-type, and wherein the average crystal grain size is less than 3.33 times the thickness of the first metal layer.
 5. The photoelectric conversion element according to claim 1, wherein the first conductive type is an n-type, and wherein the average crystal grain size is less than or equal to 2.85 times the thickness of the first metal layer.
 6. The photoelectric conversion element according to claim 1, wherein the first conductive type is an n-type, and wherein the average crystal grain size is greater than or equal to 1.55 times and less than or equal to 2.85 times the thickness of the first metal layer.
 7. The photoelectric conversion element according to claim 1, wherein the first conductive type is a p-type, and wherein the average crystal grain size is less than or equal to 3.3 times the thickness of the first metal layer.
 8. The photoelectric conversion element according to claim 1, wherein the first conductive type is a p-type, and wherein the average crystal grain size is greater than 1.5 times and less than or equal to 2.95 times the thickness of the first metal layer.
 9. The photoelectric conversion element according to claim 1, wherein the first conductive type is a p-type, and wherein the average crystal grain size is greater than or equal to 1.53 times and less than or equal to 2.15 times the thickness of the first metal layer.
 10. The photoelectric conversion element according to claim 1, wherein the second electrode includes a second transparent conductive layer formed on the second non-crystalline semiconductor layer, and a second metal layer formed on the second transparent conductive layer, wherein the second metal layer includes a plurality of metal crystal grains, wherein a contact area between the second electrode and the second non-crystalline semiconductor layer is greater than or equal to 1 time a contact area between the first electrode and the first non-crystalline semiconductor layer, and wherein an average value of the average crystal grain size of the metal crystal grain in the first metal layer, and the average crystal grain size of the metal crystal grain in the second metal layer, is greater than 1.5 times and less than or equal to 2.15 times the thickness of the first metal layer and the second metal layer. 